To shed more light on the mechanisms of UV-induced hydrogen-atom-transfer processes in heterocyclic molecules, phototautomeric thione → thiol reactions were investigated for thione compounds isolated in low-temperature Ar as well as in n-H2 (normal hydrogen) matrices. These studies concerned thione compounds with a five-membered heterocyclic ring and thione compounds with a six-membered heterocyclic ring. The experimental investigation of 2-thioimidazole and 3-thio-1,2,4-triazole (thione compounds with a five-membered heterocyclic ring) revealed that for the compounds isolated in solid n-H2 only trace amounts of thiol photoproducts were photogenerated; even though for the same compounds isolated in the solid Ar matrix, the thione → thiol photoconversion was nearly total. In contrast to that, for 3-thiopyridazine and 2-thioquinoline (thione compounds with a six-membered heterocyclic ring) isolated in solid n-H2, the UV-induced thione → thiol conversion occurred with the yield reaching 25-50% of the yield of the analogous process observed for the same species isolated in solid Ar. The obtained experimental results allow us to conclude that the dissociation-association mechanism nearly exclusively governs the phototransformation in thione heterocycles with high barriers for tautomerization (such as thione compounds with a five-membered ring), whereas the strictly intramolecular hydrogen-atom shift contributes to the mechanism of hydrogen-atom transfer in thione heterocycles with lower barriers (such as thione compounds with a six-membered ring).